On the coupling of solvent characteristics to the electronic structure of solute molecules

Abstract

We present the results of a theoretical investigation focusing on the solvent structure surrounding the −1, 0 and +1 charged species of F, Cl, Br and I halogen atoms and F₂, Cl₂, Br₂ and I₂ di-halogen molecules in a methanol solvent and its influence on the electronic structure of the solute molecules. Our results show a large stabilizing effect arising from the solute–solvent interactions. Well-formed first solvation shells are observed for all species, the structure of which is strongly influenced by the charge of the solute species. Detailed analysis reveals that coordination number, CN, solvent orientation, θ, and solute–solvent distance, d, are important structural characteristics which are coupled to changes in the electronic structure of the solute. We propose that the fundamental chemistry of any solute species is generally regulated by these solvent degrees of freedom.